TW202020111A - Materials for organic electroluminescent devices - Google Patents

Abstract

The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices which comprise these compounds.

Description

Materials for organic electroluminescent devices

The present invention relates to a compound of formula (1), use of the compound in an electronic device, and an electronic device including the compound of formula (1). The present invention further relates to a method for preparing a compound of formula (1) and a formulation containing one or more compounds of formula (1).

The research and development of functional compounds used in electronic devices is the subject of current in-depth research. Specifically, the objective is to develop compounds that can achieve improved properties of electronic devices at one or more relevant points, such as the power efficiency and lifetime of the device and the color coordinates of the emitted light.

According to the invention, the term electronic device means in particular organic integrated circuits (OIC), organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting transistors (OLET), organic solar cells (OSC), Organic optical detector, organic photoreceptor, organic field quenching device (OFQD), organic light-emitting electrochemical cell (OLEC), organic laser diode (O-laser) and organic electroluminescent device (OLED).

Of particular interest is the provision of compounds used in the last-mentioned electronic device called OLED. The general structure and functional principle of OLED are known to those skilled in the art, and are described in, for example, US 4539507.

The performance data on OLEDs still need to be further improved, especially considering the wide commercial use in display devices or as light sources, for example. In this regard, especially important are the lifetime, efficiency and operating voltage of the OLED and the color value achieved. Specifically, in the case of blue-emitting OLEDs, there is potential for improvement with regard to the lifetime and efficiency of the device.

An important starting point to achieve these improvements is to select the emitter compound and host compound used in the electronic device.

Various compounds are known from the blue fluorescent emission system of the prior art. Arylamines containing one or more condensed aryl groups are known from the prior art. Arylamines containing dibenzofuran groups (as disclosed in US 2017/0012214) or indenodibenzofuran groups (as disclosed in CN 10753308 or CN107573925) are also known from the prior art.

However, there is still a need for other fluorescent emitters, especially blue fluorescent emitters, which can be used in OLEDs and produce OLEDs that have excellent properties in terms of lifetime, color emission, and efficiency. More specifically, there is a need to combine blue fluorescent emitters with extremely high efficiency, excellent lifetime, suitable color coordinates, and high color purity.

Furthermore, it is known that OLEDs can comprise different layers, which can be applied by vapor deposition in a vacuum chamber or by treatment from solution. Vapor deposition-based methods produce good results, but these methods are complicated and expensive. Therefore, there is also a need for OLED materials that can be easily and reliably processed from solution. In this case, the materials should have good solubility properties in the solution containing them. In addition, the OLED material treated from solution itself should be able to be oriented in the deposited film to improve the overall efficiency of the OLED. The term orientation here means the horizontal molecular orientation of the compound, as explained in Zhao et al., Horizontal molecular orientation in solution-processed organic light-emitting diodes, Appl. Phys. Lett. 106063301, 2015.

Therefore, the present invention is based on the technical objective of providing compounds that are suitable for electronic devices (such as OLEDs), more specifically as blue fluorescent emitters or matrix materials, and are suitable for vacuum processing or solution processing.

In the study of novel compounds used in electronic devices, it has now been found that compounds of formula (1) as defined below are very suitable for electronic devices. Specifically, it achieves one or more, preferably all, of the technical goals mentioned above.

Therefore, the present invention relates to the compound of formula (1),

The following applies to the symbols and subscripts used: Ar ¹ and Ar ^N are the same or different at each occurrence and are selected from aromatic or heteroaromatic ring systems with 5 to 60 aromatic ring atoms, which in each case The following may be substituted by one or more groups R; E ¹ is selected from -BR ⁰ -, -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -O-, -C(R ⁰ ) ₂ -S-, -R ⁰ C=CR ⁰ -, -R ⁰ C=N-, Si(R ⁰ ) ₂ , -Si(R ⁰ ) ₂ -Si(R ⁰ ) ₂ -, -C(=O)-, -C(=NR ⁰ )-, -C(=C(R ⁰ ) ₂ )-, -O-, -S-, -S(=O)-, -SO ₂ -, -N(R ⁰ )-, -P(R ⁰ )- and -P((=O)R ⁰ )-; or E ¹ system The group of (E-1),

Where the symbol * in formula (E-1) indicates the corresponding group E ¹ in formula (1); and E ⁰ is selected from the group consisting of: single bond, -BR ^0- , -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -O-, -C(R ⁰ ) ₂ -S-, -R ⁰ C=CR ⁰ -, -R ⁰ C=N-, Si(R ⁰ ) ₂ , -Si(R ⁰ ) ₂ -Si(R ⁰ ) ₂ -, -C(=O)-, -C(= NR ⁰ )-, -C(=C(R ⁰ ) ₂ )-, -O-, -S-, -S(=O)-, -SO ₂ -, -N(R ⁰ )-, -P( R ⁰ )- and -P((=O)R ⁰ )-; E ² is selected from the group consisting of: -O-, -S-, -S(=O)- And -SO ₂ -; R ⁰ to R ⁵ represent H, D, F, Cl, Br, I, CHO, CN, N(Ar) ₂ , C(=O)Ar, P(=O)(Ar) ₂ , S(=O)Ar, S(=O) ₂ Ar, NO ₂ , Si(R) ₃ , B(OR) ₂ , OSO ₂ R; with 1 to 40 C Atom straight-chain alkyl, alkoxy or thioalkyl or branched or cyclic alkyl, alkoxy or thioalkyl having 3 to 40 C atoms, each of which may be composed of one or more groups Group R, where in each case one or more non-adjacent CH ₂ groups can be replaced by RC=CR, C≡C, Si(R) ₂ , Ge(R) ₂ , Sn(R) ₂ , C=O , C=S, C=Se, P(=O)(R), SO, SO ₂ , O, S or CONR, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN Or NO ₂ substitution; an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R in each case; or having 5 to 60 aromatic ring atoms Aryloxy group, which may be substituted by one or more groups R, wherein two adjacent substituents R ⁰ , and/or two adjacent substituents R ¹ , and/or two adjacent substituents R ² , and/ Or two adjacent substituents R ³ , and/or two adjacent substituents R ⁴ , and/or two adjacent substituents R ⁵ may form a monocyclic or polycyclic, aliphatic ring system, or aromatic ring system, which may be One or more groups R are substituted; m at each occurrence is the same or different represents an integer selected from 0, 1 or 2; n, q at each occurrence is the same or different represents selected from 0, 1, 2 , 3 or 4 integer; p in each occurrence is the same or different represents an integer selected from 0, 1, 2 or 3; R in each occurrence is the same or different represents H, D, F, Cl , Br, I, CHO, CN, N(Ar) ₂ , C(=O)Ar, P(=O)(Ar) ₂ , S(=O)Ar, S(=O) ₂ Ar, NO ₂ , Si(R') ₃ , B(OR') ₂ , OSO ₂ R ^' ; linear alkyl, alkoxy or thioalkyl having 1 to 40 C atoms or having 3 to 40 C atoms Branched or cyclic alkyl, alkoxy or thioalkyl, each of which may be substituted by one or more groups R′, wherein in each case one or more non-adjacent CH ₂ groups may be substituted by R′C =CR', C≡C, Si(R') ₂ , Ge(R') ₂ , Sn(R') ₂ , C=O, C=S, C=Se, P(=O)(R') , SO, SO ₂ , O, S, or CONR′ and one or more of the H atoms can be replaced by D, F, Cl, Br, I, CN, or NO ₂ ; aromatic groups with 5 to 60 aromatic ring atoms Or a heteroaromatic ring system, which may be substituted by one or more groups R′ in each case; or an aryloxy group having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R′ Substitution, where two adjacent substituents R may form a monocyclic or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more groups R′; Ar is the same or different in every occurrence An aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which in each case may also be substituted by one or more groups R′; R ^′ represents H the same or differently at each occurrence , D, F, Cl, Br, I, CN; linear alkyl, alkoxy or thioalkyl having 1 to 20 C atoms; or branched or cyclic having 3 to 20 C atoms Alkyl, alkoxy or thioalkyl, where in each case one or more non-adjacent CH ₂ groups can be replaced by SO, SO ₂ , O, S and one or more H atoms can be replaced by D, F , Cl, Br or I substitution; or an aromatic or heteroaromatic ring system with 5 to 24 C atoms.

In the sense of the present invention, adjacent substituents are substituents bonded to atoms directly connected to each other or to the same atom.

In addition, the following definitions of chemical groups apply to the purposes of this application:

In the sense of the present invention, aryl groups contain 6 to 60 aromatic ring atoms, preferably 6 to 40 aromatic ring atoms, more preferably 6 to 20 aromatic ring atoms; in the sense of the present invention, heteroaromatic The group contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is a heteroatom. The hetero atom is preferably selected from N, O and S. This represents the basic definition. If other preferred ones are indicated in the description of the present invention (for example, regarding the number of aromatic ring atoms or heteroatoms present), these definitions also apply.

The aryl or heteroaryl group herein means a simple aromatic ring (i.e., benzene) or a simple heteroaromatic ring (such as pyridine, pyrimidine, or thiophene) or a condensed (fused ring) aromatic or heteroaromatic polycyclic ring (such as naphthalene, Phenanthrene, quinoline or carbazole). In the meaning of this application, a condensed (fused ring) aromatic or heteroaromatic polycyclic ring system consists of two or more simple aromatic or heteroaromatic rings condensed with each other.

In each case, an aryl or heteroaryl group which may be substituted by the groups mentioned above and which can be connected to an aromatic or heteroaromatic ring system via any desired position means in particular a group derived from: benzene, Naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, beryllium, perylene, fluoranthene, benzoanthracene, benzophenanthrene, fused tetraphenylene, fused pentabenzene, benzopyrene, furan, benzofuran, isobenzofuran, Dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo -5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphtho Imidazole, phenimidazole, pyridoimidazole, pyrazinoimidazole, quinoxadenoimidazole, oxazole, benzoxazole, naphthoxazole, anthraoxazole, phenoxazole, isoxazole, 1, 2-thiazole, 1,3-thiazole, benzothiazole, triazine, benzotriazine, pyrimidine, benzopyrimidine, quinoxaline, pyrazine, phenazine, naphthyridine, azacarbazole, benzoxazoline , Phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1, 2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1, 3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1 , 2,3,4-tetrazine, 1,2,3,5-tetrazine, purine, pyridine, indazine and benzothiadiazole.

According to the definition of the present invention, aryloxy means an aryl group bonded via an oxygen atom as defined above. Similar definitions apply to heteroaryloxy.

In the sense of the present invention, the aromatic ring system contains 6 to 60 C atoms, preferably 6 to 40 C atoms, more preferably 6 to 20 C atoms in the ring system. In the sense of the present invention, a heteroaromatic ring system contains 5 to 60 aromatic ring atoms, preferably 5 to 40 aromatic ring atoms, more preferably 5 to 20 aromatic ring atoms, at least one of which is Heteroatom. The hetero atom is preferably selected from N, O and/or S. In the sense of the present invention, an aromatic or heteroaromatic ring system is intended to mean that it does not necessarily contain only aryl or heteroaryl groups, on the contrary, in which a plurality of aryl groups or heteroaryl groups may be composed of non-aromatic units (preferably less than 10 % Of atoms other than H) (eg sp ³ hybrid C, Si, N or O atoms, sp ² hybrid C or N atoms or sp hybrid C atoms) connected systems. Thus, for example, in the sense of the present invention, systems such as 9,9'-spirodifutilene, 9,9'-diarylstilbene, triarylamine, diaryl ether, stilbene, etc. are also intended to be considered aromatic Family ring systems, such as systems in which two or more aryl groups are connected by, for example, a linear or cyclic alkyl, alkenyl or alkynyl, or silyl group. In addition, in the sense of the present invention, a system in which two or more aryl groups or heteroaryl groups are connected to each other via a single bond is also regarded as an aromatic or heteroaromatic ring system, for example, such as Or diphenyl triazine and other systems.

In each case, an aromatic or heteroaromatic ring system having 5 to 60 aromatic atoms that can also be substituted by a group as defined above and can be connected to an aromatic or heteroaromatic ring group via any desired position In particular, it means groups derived from: benzene, naphthalene, anthracene, benzoanthracene, phenanthrene, benzophenanthrene, pyrene, dihydropyrene, beryllium, perylene, fluoranthene, benzoanthracene, fused pentabenzene, biphenyl, Bisbiphenyl, biphenyl, triphenylene, tetraphenyl, stilbene, spirodifutilene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis- or trans-indenoquino, quinoxene (truxene) , Isotruxene, spirotruxene, spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene , Isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzene Benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthalene Pyridimidazole, phenimidazole, pyridoimidazole, pyrazinoimidazole, quinoxadenoimidazole, oxazole, benzoxazole, naphthoxazole, anthracoxazole, phenanthoxazole, isoxazole, 1 ,2-thiazole, 1,3-thiazole, benzothiazole, triazine, benzotriazine, pyrimidine, benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene , 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazapyrene, Pyrazine, phenazine, phenoxazine, phenothiazine, fluorubin, naphthyridine, azacarbazole, benzotriline, phenanthroline, 1,2,3-triazole, 1,2 ,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole , 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5 -Tetrazine, purine, pyridine, indazine and benzothiadiazole or combinations of these groups.

For the purposes of the present invention, a linear alkyl group having 1 to 40 C atoms or a branched or cyclic alkyl group having 3 to 40 C atoms or an alkenyl or alkynyl group having 2 to 40 C atoms (In addition, individual H atoms or CH ₂ groups may be substituted with the above-mentioned groups under the definition of group) Preferably, the following groups are meant: methyl, ethyl, n-propyl, isopropyl , N-butyl, isobutyl, second butyl, third butyl, 2-methylbutyl, n-pentyl, second pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, new Hexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, vinyl, propenyl , Butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl Group, pentynyl, hexynyl or octynyl. The alkoxy or thioalkoxy having 1 to 40 C atoms preferably means methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, iso Butoxy, second butoxy, third butoxy, n-pentyloxy, second pentyloxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptyloxy, cyclo Heptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio, ethylthio, n-propyl Sulfur, isopropylthio, n-butylthio, isobutylthio, second butylthio, third butylthio, n-pentylthio, second pentylthio, n-hexylthio, cyclohexylthio, N-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio Group, vinylthio group, propylenethio group, butenethio group, pentenethio group, cyclopentenethio group, hexenylthio group, cyclohexenethio group, heptenethio group, cycloheptenethio group, octene Sulfur, cyclooctenylthio, acetylenethio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio.

For the purposes of this application, the expression that two or more groups may form a ring with each other is intended to mean in particular that the two groups are connected to each other by a chemical bond. This system is illustrated by the following diagram:

In addition, however, the expression mentioned above is also intended to mean that in the case where one of the two groups represents hydrogen, the second group is bonded at the position where the hydrogen atom is bonded, and forms a ring. This system is illustrated by the following diagram:

According to a preferred embodiment, the group E ¹ is selected from -C(R ⁰ ) ₂ -, -Si(R ⁰ ) ₂ -, -O-, -S-, -N( R ⁰ )-; or E ¹ is a group of formula (E-1),

Where the symbol * in formula (E-1) indicates the corresponding group E ¹ in formula (1) and where E ⁰ has the same meaning as above.

According to an excellent embodiment, the group E ¹ represents -C(R ⁰ ) ₂ -.

According to another excellent embodiment, the group E ¹ represents a group of formula (E-1), wherein E ⁰ represents a single bond or -C(R ⁰ ) ₂ -.

Preferably, the group E ² is selected from -O- or -S- the same or different at each occurrence. Very well, the group E ² represents -O-.

Preferably, Ar ^N represents phenyl, biphenyl, stilbene, spirobifutene, naphthalene, phenanthrene, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrimidine, pyrazine, triazine, triazine, benzene Pyridine, benzoxazine, benzopyrimidine, or quinazoline, or a combination of two to six of these groups, each of which may be substituted with one or more groups R.

Very preferably, Ar ^N represents phenyl, biphenyl, stilbene, naphthalene, phenanthrene, dibenzofuran, dibenzothiophene, carbazole, or a combination of two to six of these groups, each of which can be composed of a Or multiple groups R substituted.

More preferably, Ar ^N represents groups of formulas (ArN-1) to (ArN-22) shown in the following table:

Among them in formulas (ArN-1) to (ArN-22):-the dotted bond indicates the bonding to the nitrogen of the structure of formula (1);-the group R ^N in formula (ArN-14) appears every time When the same or different represents H, D; linear alkyl having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or having 3 to 40, preferably 3 to 20, more preferably 3 to A branched or cyclic alkyl group of 10 C atoms, each of which may be substituted by one or more groups R, wherein in each case one or more non-adjacent CH ₂ groups may be substituted by RC=CR, C≡C , C=O, C=S, SO, SO ₂ , O or S, and one or more of the H atoms can be replaced by D, F or CN; having 5 to 60, preferably 5 to 40, more preferably 5 to 30. A particularly preferred aromatic or heteroaromatic ring system of 5 to 18 aromatic ring atoms may be substituted by one or more groups R in each case, and two adjacent substituents R ^N may form a single ring Or polycyclic, aliphatic ring system or aromatic ring system, which may be substituted by one or more groups R, where R has the same meaning as above;-formula (ArN-12) and (ArN-19) to ( The group R ^0a in ArN-22) has the same meaning as the group R ⁰ as defined above; and-the groups of formula (ArN-1) to (ArN-22) can be The group R is substituted, and the group R has the same meaning as above.

According to a preferred embodiment, the group Ar ¹ represents an aromatic or heteroaromatic ring system selected from the same or different at each occurrence: phenyl, biphenyl, stilbene, spirobistilbene, naphthalene, phenanthrene, di Benzofuran, dibenzothiophene, carbazole, pyridine, pyrimidine, pyrazine, pyrazine, triazine, benzopyridine, benzopyrazine, benzopyrimidine, quinazoline or both of these groups The combination of up to six, each of which may be substituted by one or more groups R.

Very preferably, the group Ar ¹ represents the aromatic or heteroaromatic ring system selected from the same or different at each occurrence: phenyl, biphenyl, stilbene or naphthalene, each of which may be composed of one or more groups R substitution; or a combination of two to six groups selected from phenyl, biphenyl, stilbene, or naphthalene, each of which may be substituted with one or more groups R.

Examples of suitable groups Ar ^{1 are} groups of formulae (Ar1-1) to (Ar1-22) shown below:

Where in formulas (Ar1-1) to (Ar1-22):-the dotted bond indicates the bonding to the structure of formula (1);-the group R ^N in formula (Ar1-14) has the same as above Definition;-The group R ^0a has the same definition as above; and-The groups of formula (Ar1-1) to (Ar1-22) may be substituted by the group R at each free position, the group R has Same meaning as above.

其中符號Ar^N 、E¹ 、E² 、Ar¹ 、R¹ 至R⁵ 及下標m、n、p及q具有與上文相同之含義。Preferably, the compound of formula (1) is selected from compounds of formula (2),

The symbols Ar ^N , E ¹ , E ² , Ar ¹ , R ¹ to R ⁵ and the subscripts m, n, p and q have the same meanings as above.

其中符號Ar^N 、E² 、Ar¹ 、R⁰ 、R¹ 至R⁵ 及下標m、n、p及q具有與上文相同之含義。Very preferably, the compound of formula (1) is selected from compounds of formula (3),

The symbols Ar ^N , E ² , Ar ¹ , R ⁰ , R ¹ to R ⁵ and the subscripts m, n, p and q have the same meanings as above.

其中符號Ar^N 、E² 、Ar¹ 、R⁰ 、R¹ 至R⁵ 及下標m、n、p及q具有與上文相同之含義。Preferably, the compound of formula (1) is selected from compounds of formula (4),

The symbols Ar ^N , E ² , Ar ¹ , R ⁰ , R ¹ to R ⁵ and the subscripts m, n, p and q have the same meanings as above.

其中符號Ar^N 、E² 、Ar¹ 、R⁰ 、R¹ 至R⁵ 具有與上文相同之含義。Very particularly preferably, the compound of formula (1) is selected from compounds of formula (4-1) to (4-4),

The symbols Ar ^N , E ² , Ar ¹ , R ⁰ , R ¹ to R ⁵ have the same meanings as above.

其中符號Ar^N 、E² 、Ar¹ 、R⁰ 及R¹ 具有與上文相同之含義。According to a preferred embodiment, the compounds of formulae (4-1) to (4-4) are selected from compounds of formulae (4-1a) to (4-4a),

The symbols Ar ^N , E ² , Ar ¹ , R ⁰ and R ¹ have the same meanings as above.

其中符號Ar^N 、E² 、Ar¹ 及R⁰ 具有與上文相同之含義。According to another preferred embodiment, the compounds of formulae (4-1) to (4-4) are selected from compounds of formulae (4-1b) to (4-4b),

The symbols Ar ^N , E ² , Ar ¹ and R ⁰ have the same meanings as above.

Preferably, the groups R ⁰ and R ^0a represent H, D, F, CN the same or different at each occurrence; having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms Chain alkyl; or a branched or cyclic alkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms, each of which may be substituted by one or more groups R, in which each In one case, one or more non-adjacent CH ₂ groups may be replaced by RC=CR, C≡C, C=O, C=S, SO, SO ₂ , O, or S and one or more H atoms may be replaced by D, F , Cl, Br, I, CN or NO ₂ substitution; an aromatic or heteroaromatic ring system having 5 to 60, preferably 5 to 40, more preferably 5 to 25, even more preferably 5 to 18 aromatic ring atoms , Which may be substituted by one or more groups R in each case; two adjacent substituents R ⁰ and/or R ^0a may form a monocyclic or polycyclic, aliphatic ring system or aromatic ring system, which may be One or more groups R are substituted.

Very preferably, the groups R ⁰ and R ^0a represent H at the same time or differently at each occurrence, a linear alkyl group having 1 to 10 C atoms or a branched or cyclic group having 3 to 10 C atoms Alkyl groups, each of which may be substituted by one or more groups R, wherein one or more H atoms may be replaced by D, F, Cl, Br, I, CN or NO ₂ ; aromatic having 5 to 18 aromatic ring atoms A family or heteroaromatic ring system, which in each case may be substituted by one or more groups R, where two adjacent substituents R ⁰ and/or R ^0a may form a monocyclic or polycyclic, aliphatic ring system or An aromatic ring system, which may be substituted with one or more groups R.

More preferably, the groups R ⁰ and/or R ^0a represent the same or different linear alkyl groups having 1 to 10 C atoms at each occurrence, which may be substituted by one or more groups R; or have 5 Aromatic or heteroaromatic ring systems of up to 18 aromatic ring atoms, which in each case may be substituted by one or more groups R, where two adjacent substituents R ⁰ may form a monocyclic or polycyclic, aliphatic A family ring system or an aromatic ring system, which may be substituted with one or more groups R.

Very particularly preferably, R ⁰ at each occurrence represents the same or differently methyl or phenyl groups, which can be substituted by one or more groups R.

Very particularly preferably, the group R ^0a at each occurrence is the same or different and represents a straight-chain alkyl group having 1 to 10 C atoms, which can be substituted by one or more groups R.

According to a preferred embodiment, the groups of the formula (ArN-12) and (Ar1-12) include 1 or 2 groups R ^0a , which represents having 3 to 10, preferably 5 to 10, more preferably 6 to 10 Linear alkyl group of C atom; and the groups of formula (ArN-19) to (ArN-22), (Ar1-19) to (Ar1-22) include 1, 2, 3 or 4 groups R ^0a , It represents a linear alkyl group having 3 to 10, preferably 5 to 10, more preferably 6 to 10 C atoms.

Preferably, R ¹ to R ⁵ represent H, D, F, CN, N(Ar) ₂ , Si(R) _{3 the} same or different at each occurrence; having 1 to 40, preferably 1 to 20, More preferably, a linear alkyl group, an alkoxy group or a thioalkyl group of 1 to 10 C atoms; or a branched or cyclic group having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms Alkyl, alkoxy or thioalkyl, each of which may be substituted by one or more groups R, wherein in each case one or more non-adjacent CH ₂ groups may be replaced by RC=CR, C≡C, C =O, C=S, SO, SO ₂ , O, or S and one or more H atoms can be replaced by D, F, Cl, Br, I, CN, or NO ₂ ; having 5 to 60, preferably 5 to 40. An aromatic or heteroaromatic ring system of more preferably 5 to 25, even more preferably 5 to 18 aromatic ring atoms, which may be substituted by one or more groups R in each case; or having 5 to 60 , Preferably 5 to 40, more preferably 5 to 25, even more preferably 5 to 18 aryloxy groups of aromatic ring atoms, which may be substituted by one or more groups R, of which two adjacent substituents R ¹ , And/or two adjacent substituents R ² , and/or two adjacent substituents R ³ , and/or two adjacent substituents R ⁴ , and/or two adjacent substituents R ⁵ may form a monocyclic or polycyclic ring , An aliphatic ring system or an aromatic ring system, which may be substituted by one or more groups R.

More preferably, R ¹ represents H, D, F, CN the same or different at each occurrence; a linear alkyl group having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms; or A branched or cyclic alkyl group having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms, each of which may be substituted by one or more groups R; having 5 to 60, preferably 5 to 40. More preferably, an aromatic or heteroaromatic ring system of 5 to 25, even more preferably 5 to 18 aromatic ring atoms may be substituted by one or more groups R in each case.

According to a preferred embodiment, R ¹ is H.

According to another preferred embodiment, the compound of formula (1) comprises at least one group R ¹ selected from an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms.

When the compound of formula (1) contains at least one group R ¹ selected from an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, then R ¹ preferably represents selected from phenyl, biphenyl, Fusel, spirobifuran, naphthalene, phenanthrene, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrimidine, pyrazine, pyrazine, triazine, benzopyridine, benzazine, benzopyrimidine, quinoline The groups of oxazoline or a combination of two to six of these groups may each be substituted with one or more groups R.

When the compound of formula (1) contains at least one group R ¹ selected from an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, then R ¹ very well represents a group selected from: benzene Group, biphenyl, stilbene and naphthalene, each of which may be substituted by one or more groups R; or a combination of two to six groups selected from the group consisting of phenyl, biphenyl, stilbene or naphthalene, each of which may be Or multiple groups R substituted.

Particularly preferably, the compound of formula (1) contains at least one group R ¹ , which represents a group selected from formulae (Ar1-1) to (Ar1-22) as represented above. Very particularly preferably, the compound of formula (1) contains at least one group R ¹ , which represents a group selected from the formulae (Ar1-19) to (Ar1-22) as indicated above.

According to a preferred embodiment, the groups R ² to R ⁵ represent H, D, F, CN the same or different at each occurrence; having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms Linear alkyl groups; or branched or cyclic alkyl groups having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms, each of which may be substituted by one or more groups R; or having An aromatic or heteroaromatic ring system of 5 to 18 aromatic ring atoms can be substituted by one or more groups R in each case. Preferably, R ² to R ⁵ represent H at the same time or differently at each occurrence, a linear alkyl group having 1 to 10 C atoms or a branched or cyclic alkyl group having 3 to 10 C atoms , Each of which may be substituted by one or more groups R; or an aromatic or heteroaromatic ring system having 5 to 18 aromatic ring atoms, which may be substituted by one or more groups R in each case. Very particularly preferably, R ² to R ⁵ represent H.

According to a preferred embodiment, R represents H, D, F, CN, N(Ar) ₂ , Si(R′) _{3 the} same or different each time it appears; having 1 to 40, preferably 1 to 20, more Straight chain alkyl, alkoxy or thioalkyl having 1 to 10 C atoms; or branched or cyclic alkyl having 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms Group, alkoxy group or thioalkyl group, each of which may be substituted by one or more groups R′, wherein in each case one or more non-adjacent CH ₂ groups may be replaced by R′C=CR′, C≡ C, C=O, C=S, SO, SO ₂ , O or S and one or more of the H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ ; with 5 to 60, more An aromatic or heteroaromatic ring system of preferably 5 to 40, more preferably 5 to 25, even more preferably 5 to 18 aromatic ring atoms, which may be substituted by one or more groups R′ in each case; or An aryloxy group having 5 to 60, preferably 5 to 40, more preferably 5 to 25, even more preferably 5 to 18 aromatic ring atoms, which may be substituted by one or more groups R′, two of which are adjacent The substituent R may form a monocyclic or polycyclic ring, an aliphatic ring system or an aromatic ring system, which may be substituted by one or more groups R′.

According to a preferred embodiment, R ^′ represents H, D, F, Cl, Br, I, CN the same or different at each occurrence; linear alkyl having 1 to 10 C atoms or having 3 to 10 C atoms are branched or cyclic alkyl groups or aromatic or heteroaromatic ring systems with 5 to 18 C atoms.

The following compounds are examples of compounds of formula (1):

The compounds of the present invention can be synthesized by procedures known to those skilled in the art, such as bromination, Suzuki coupling, Ullmann coupling, and Hartwig-Buchwald coupling (Hartwig- Buchwald coupling) etc. to prepare. Examples of suitable synthesis methods are shown in general scheme 1 below.

Schematic 1

Step 1- Synthesis of the first intermediate

Step 2- Synthesis of the second intermediate

Step 3- Synthesis of compound of formula (1)

Scheme 2 Step 1- Synthesis of the first intermediate ( same as Step 1 of Diagram 1 ) Step 2- Synthesis of the second intermediate

Step 3- Synthesis of the third intermediate

Step 4- Synthesis of compound of formula (1)

酸酯)。In the schematic diagrams 1 and 2, the symbols Ar ¹ , Ar ^N , E ² , R ¹ , R ⁰ and R have the same meaning as above, and the symbols X ¹ , X ² and X ³ represent a leaving group (such as halogen or

Acid ester).

Therefore, the present invention relates to a method for synthesizing the compound of the present invention, which includes the step of reacting an aminated oxadiindenofungal derivative with an indenodibenzofuran derivative.

For treating the compound of the present invention from the liquid phase, for example, by spin coating or by a printing method, a formulation of the compound of the present invention is necessary. Such formulations can be, for example, solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents can be preferably used. Suitable and preferred solvents are, for example, toluene, anisole, o-, m- or p-xylene, methyl benzoate, mesityl, tetrahydronaphthalene, o-dimethoxybenzene, THF, methyl -THF, THP, chlorobenzene, dioxane, phenoxytoluene (specifically 3-phenoxytoluene), (-)-fenone, 1,2,3,5-tetratoluene, 1,2, 4,5-tetratoluene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4 -Dimethyl anisole, 3,5-dimethyl anisole, acetophenone, α-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclic Hexylbenzene, decahydronaphthalene, dodecylbenzene, ethyl benzoate, dihydroindene, NMP, p-dill hydrocarbon, phenethyl ether, 1,4-diisopropylbenzene, dibenzyl ether, di Ethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol di Methyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane or a mixture of these solvents.

Therefore, the present invention relates to a formulation comprising the compound of the present invention and at least one other compound. The other compound may be, for example, a solvent, specifically one of the solvents mentioned above or a mixture of such solvents. However, the other compound may also be at least one other organic or inorganic compound also used in electronic devices, such as an emitting compound, specifically a phosphorescent dopant, and/or other host materials. Suitable emitting compounds and other matrix materials are indicated below in conjunction with organic electroluminescent devices. This other compound may also be a polymer.

The compounds and mixtures of the present invention are suitable for electronic devices. Electronic device means herein a device comprising at least one layer comprising at least one organic compound. However, the components herein may also comprise inorganic materials or layers consisting entirely of inorganic materials.

Therefore, in addition, the invention relates to the use of the compounds or mixtures of the invention for electronic devices, in particular for organic electroluminescent devices.

In addition, the present invention also relates to an electronic device comprising at least one of the compounds or mixtures of the present invention mentioned above. The preferred ones described above for compounds are also applicable to electronic devices.

The electronic device is preferably selected from the group consisting of organic electroluminescent devices (OLED, PLED), organic integrated circuits (O-IC), organic field effect transistors (O-FET), organic thin film transistors (O -TFT), organic light-emitting transistor (O-LET), organic solar cell (O-SC), organic dye-sensitized solar cell, organic optical detector, organic photoreceptor, organic quenching device (O-FQD) , Light-emitting electrochemical cell (LEC), organic laser diode (O-laser) and "organic plasma emission device" (DM Koller et al., Nature Photonics 2008 , 1-4), preferably organic electroluminescent Light emitting devices (OLED, PLED), specifically phosphorescent OLEDs.

The organic electroluminescent device includes a cathode, an anode, and at least one emission layer. In addition to these layers, it may also include other layers, such as, in each case, one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, exciton blocking Layer, electron blocking layer and/or charge generating layer. An interlayer with, for example, an exciton blocking function can also be introduced between the two emission layers. However, it should be noted that each of these layers does not necessarily have to exist. The organic electroluminescent device herein may include one emission layer or a plurality of emission layers. If there are a plurality of emission layers, these emission layers preferably have a total of a plurality of emission maximums between 380 nm and 750 nm, so as to produce white emission as a whole, that is, use in the emission layer that can emit fluorescence or phosphorescence Various emitting compounds. A better one is a system with three emission layers, of which three layers exhibit blue, green, and orange or red emission (for the basic structure, see (for example) WO 2005/011013). These can be fluorescent or phosphorescent emission layers or hybrid systems, where the fluorescent and phosphorescent emission layers are combined with each other.

Depending on the precise structure and substitution, the compounds of the present invention according to the embodiments indicated above can be used in various layers. Preferably, it is an organic electroluminescence device comprising the compound of formula (1) or a fluorescent emitter, an emitter displaying TADF (thermally activated delayed fluorescence), a matrix material of the fluorescent emitter according to the preferred embodiment. Particularly preferred are organic electroluminescent devices, which comprise the compound of formula (1) or according to a preferred embodiment as a fluorescent emitter, more specifically a blue generating fluorescent compound.

Depending on the exact substitution, the compound of formula (1) can also be used in the electron transport layer and/or electron blocking layer or exciton blocking layer and/or hole transport layer. The preferred embodiments indicated above also apply to the use of these materials in organic electronic devices.

The compounds of the present invention are particularly suitable for use as blue emitting emitter compounds. The electronic device of interest may include a single emission layer including the compound of the present invention, or it may include two or more emission layers. Other emission layers herein may include one or more compounds of the present invention or other compounds.

If the compound of the present invention is used as a fluorescent emitting compound in the emitting layer, it is preferably used in combination with one or more matrix materials. The matrix material herein means a material that is preferably present as an essential component in the emission layer and does not emit light when the device is in operation.

The ratio of emissive compounds in the mixture of emissive layers is between 0.1% and 50.0%, preferably between 0.5% and 20.0%, particularly preferably between 1.0% and 10.0%. Correspondingly, the ratio of one or more matrix materials is between 50.0% and 99.9%, preferably between 80.0% and 99.5%, particularly preferably between 90.0% and 99.0%.

For the purposes of this application, if the compound is applied from the gaseous phase, the description in terms of% means vol. %, and if the compound is applied from solution, it means% by weight.

酸衍生物(例如根據WO 2006/117052)或苯并蒽(例如根據WO 2008/145239)。尤佳基質材料係選自以下類別：寡伸芳基，包含萘、蒽、苯并蒽及/或芘或該等化合物之阻轉異構物；寡伸芳基伸乙烯基、酮、氧化膦及亞碸。極佳基質材料係選自以下類別：寡伸芳基，包含蒽、苯并蒽、苯并菲及/或芘或該等化合物之阻轉異構物。在本發明之意義上，寡伸芳基意欲意指其中至少三個芳基或伸芳基彼此鍵結之化合物。Preferred matrix materials for use in combination with fluorescent emitting compounds are selected from the following categories: oligomeric aryl groups (eg 2,2',7,7'-tetraphenylspirobifuran or dinaphthylanthracene according to EP 676461) , In particular, oligomeric aryl groups, oligomeric aryl groups containing condensed aromatic groups (eg DPVBi or spiro-DPVBi according to EP 676461); polypodal metal complexes (eg according to WO 2004/ 081017), hole-conducting compounds (for example according to WO 2004/058911); electron-conducting compounds, specifically ketones, phosphine oxides, sulfoxides, etc. (for example according to WO 2005/084081 and WO 2005/084082); atropisomers (For example according to WO 2006/048268),

Acid derivatives (for example according to WO 2006/117052) or benzanthracene (for example according to WO 2008/145239). The preferred matrix materials are selected from the following categories: oligoarylene groups, including naphthalene, anthracene, benzoanthracene and/or pyrene or atropisomers of these compounds; Arrogance. An excellent matrix material is selected from the following categories: oligomeric aryl groups, including anthracene, benzoanthracene, benzophenanthrene and/or pyrene or atropisomers of these compounds. In the sense of the present invention, oligoaryl group is intended to mean a compound in which at least three aryl groups or aryl groups are bonded to each other.

Particularly preferred matrix materials used in combination with compounds of formula (1) for use in the emission layer are shown in the table below.

If the compound of the present invention is used as a fluorescent emitting compound in the emitting layer, it can be used in combination with one or more other fluorescent emitting compounds.

In addition to the compounds of the present invention, preferred fluorescent emission systems are selected from the class of arylamines. In the sense of the present invention, arylamine means a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems directly bonded to nitrogen. At least one of the aromatic or heteroaromatic ring systems is preferably a fused ring system, and particularly preferably has at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthracene amine, aromatic anthracene diamine, aromatic pyrene amine, aromatic pyrene diamine, aromatic beryllium amine or aromatic beryllium diamine. Aromatic anthracene means a compound in which a diarylamine group is preferably directly bonded to the anthracene group at the 9-position. Aromatic anthracene diamine means a compound in which two diaryl amine groups are preferably directly bonded to the anthracene group at the 9,10 position. Aromatic pyrene amine, pyrene diamine, beryllium amine and beryllium diamine are similarly defined, wherein the diarylamine group is preferably bonded to pyrene at the 1 position or the 1,6 position. Other preferred emission systems indeno-funamine or indeno-fujidiamine, for example according to WO 2006/108497 or WO 2006/122630; benzo-indenofunctamine or benzo-indenofunctodiamine, for example according to WO 2008/006449; And dibenzoindeno stilbene amine or dibenzo indeno stilbene diamine, for example according to WO 2007/140847; and indeno stilbene derivatives containing condensed aryl groups, which are disclosed in WO 2010/012328. Still preferred emission systems are benzoanthracene derivatives as disclosed in WO 2015/158409, anthracene derivatives as disclosed in WO 2017/036573, stilbene dimers as in WO 2016/150544 or as in WO 2017/028940 And the phenoxazine derivatives disclosed in WO 2017/028941. Also preferred is the pyrene arylamine disclosed in WO 2012/048780 and WO 2013/185871. Also preferred are the benzoindeno amines disclosed in WO 2014/037077, the benzo benzo amines disclosed in WO 2014/106522, and the indeno fluorenes disclosed in WO 2014/111269 or WO 2017/036574.

In addition to the compounds of the present invention, examples of preferred fluorescent emitting compounds are shown in the table below. These fluorescent emitting compounds can be used in combination with the compounds of the present invention in an emitting layer or can be used in another emitting layer of the same device in:

The compounds of the present invention can also be used as other layers, for example as a hole-transporting layer or a hole-transporting layer or a hole-transporting material in an electron blocking layer or as a matrix material in an emitting layer, preferably as a phosphorescent emitter Of the matrix material.

If the compound of formula (I) is used as a hole-transporting material in a hole-transporting layer, a hole-injecting layer, or an electron blocking layer, the compound can be used in the hole-transporting layer in the form of a pure material, that is, at a 100% ratio Or it can be used in combination with one or more other compounds. According to a preferred embodiment, the organic layer containing the compound of formula (I) additionally contains one or more p-dopants. The p-dopant used according to the present invention is preferably an organic electron acceptor compound capable of oxidizing one or more of the other compounds of the mixture.

Preferred examples of p-dopants are WO 2011/073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO 2009/003455, WO 2010/094378, Compounds disclosed in WO 2011/120709, US 2010/0096600 and WO 2012/095143.

If the compound of formula (I) is used in combination with a phosphorescent emitter as the matrix material in the emission layer, the phosphorescent emitter is preferably selected from the categories and examples of phosphorescent emitters indicated below. Furthermore, in this case, preferably one or more other matrix materials are present in the emission layer.

This type of so-called mixed matrix system preferably comprises two or three different matrix materials, particularly preferably two different matrix materials. Herein, it is preferable to use one of two materials as a material having hole-transporting properties and another material as a material having electron-transporting properties. The compound of formula (I) is preferably a material having hole-transporting properties.

However, the desired electron transport and hole transport properties of the mixed matrix component can also be mainly or completely combined in a single mixed matrix component, where other mixed matrix components fulfill other functions. Two different matrix materials can be present here in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, particularly preferably 1:10 to 1:1 and very particularly preferably 1:4 to 1:1 . The hybrid matrix system is preferably used in phosphorescent organic electroluminescent devices. Further details about the mixed matrix system are included in the application WO 2010/108579 in particular.

A particularly suitable matrix material that can be used in combination with the compounds of the present invention as a matrix component of a mixed matrix system is a preferred matrix material selected from phosphorescent emitters indicated below or a preferred matrix material for fluorescent emitters, depending on What kind of emitter compound is the material in the mixed matrix system.

The following indicates the generally preferred categories of materials used as corresponding functional materials in the organic electroluminescent device of the present invention.

Specifically, a suitable phosphorescent emission system is a compound that preferably emits light in the visible region when suitably excited, and additionally contains at least one atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80 atom. The phosphorescent emitter used is preferably a compound containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, specifically a compound containing iridium, platinum or copper.

For the purposes of the present invention, all luminescent iridium, platinum or copper complexes are considered phosphorescent compounds.

Examples of the aforementioned phosphorescent emitters are from WO 2000/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 2005/033244, WO 2005/019373 and US 2005/0258742 reveal. In general, all phosphorescent composites are used in phosphorescent OLEDs according to the prior art and as known to those skilled in the art are suitable for the device of the present invention in the field of organic electroluminescent devices. Those skilled in the art will also be able to use other phosphorescent compounds in combination with the compounds of the present invention for OLEDs without the steps of the present invention.

酸酯，例如根據WO 2006/117052；三嗪衍生物，例如根據WO 2010/015306、WO 2007/063754或WO 2008/056746；鋅錯合物，例如根據EP 652273或WO 2009/062578；二氮雜矽雜環戊二烯或四氮雜矽雜環戊二烯衍生物，例如根據WO 2010/054729；二氮雜磷雜雜環戊二烯(diazaphosphole)衍生物，例如根據WO 2010/054730；橋接咔唑衍生物，例如根據US 2009/0136779、WO 2010/050778、WO 2011/042107、WO 2011/088877或WO 2012/143080；聯伸三苯衍生物，例如根據WO 2012/048781；或內醯胺，例如根據WO 2011/116865或WO 2011/137951。Preferred host materials for phosphorescent emitters are aromatic ketones, aromatic phosphine oxides, or aromatic sulfides or ash, for example according to WO 2004/013080, WO 2004/093207, WO 2006/005627 or WO 2010/006680; triarylamine Carbazole derivatives such as CBP (N,N-biscarbazolylbiphenyl) or carbazole derivatives disclosed in WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851 Derivatives; indolocarbazole derivatives, for example according to WO 2007/063754 or WO 2008/056746; indenocarbazole derivatives, for example according to WO 2010/136109, WO 2011/000455 or WO 2013/041176; azacarbazole Derivatives, for example according to EP 1617710, EP 1617711, EP 1731584, JP 2005/347160; bipolar matrix materials, for example according to WO 2007/137725; silanes, for example according to WO 2005/111172; azaborole or azaborole or

Ester esters, for example according to WO 2006/117052; triazine derivatives, for example according to WO 2010/015306, WO 2007/063754 or WO 2008/056746; zinc complexes, for example according to EP 652273 or WO 2009/062578; diaza Silacyclopentadiene or tetraazasilacyclopentadiene derivatives, for example according to WO 2010/054729; diazaphosphole derivatives, for example according to WO 2010/054730; bridging Carbazole derivatives, for example according to US 2009/0136779, WO 2010/050778, WO 2011/042107, WO 2011/088877 or WO 2012/143080; Biphenyl triphenyl derivatives, for example according to WO 2012/048781; or lactamamide, For example according to WO 2011/116865 or WO 2011/137951.

In addition to the compounds of the present invention, suitable charge transport materials such as Y. Shirota et al., which can be used in the hole injection layer or hole transport layer or electron blocking layer or in the electron transport layer of the electronic device of the present invention, The compounds disclosed in Chem. Rev. 2007, 107(4), 953-1010 or other materials used in these layers according to the prior art.

Materials usable for the electron transport layer are all materials used as electron transport materials in the electron transport layer according to the prior art. Particularly suitable are aluminum complexes, such as Alq ₃ ; zirconium complexes, such as Zrq ₄ ; lithium complexes, such as Liq; benzimidazole derivatives, triazine derivatives, pyrimidine derivatives, pyridine derivatives, pyridine Azine derivatives, quinoline derivatives, quinoline derivatives, oxadiazole derivatives, aromatic ketones, amides, borane, diazaphosphorene derivatives and phosphine oxide derivatives. In addition, suitable materials are derivatives of the compounds mentioned above, as disclosed in JP 2000/053957, WO 2003/060956, WO 2004/028217, WO 2004/080975, and WO 2010/072300.

The preferred hole-transporting material that can be used in the hole-transporting layer, hole-injecting layer or electron-blocking layer in the electroluminescent device of the present invention is an indenoxylamine derivative (eg according to WO 06/122630 or WO 06/ 100896), amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (e.g. according to WO 01/049806), amine derivatives containing condensed aromatic rings (e.g. according to US 5,061,569), WO 95/09147 Revealed amine derivatives, monobenzoindenofunamine (e.g. according to WO 08/006449), dibenzoindenofenamine (e.g. according to WO 07/140847), spirobibenzoamine (e.g. according to WO 2012/034627 or WO 2013/120577), stilbene amines (eg according to applications EP 2875092, EP 2875699 and EP 2875004), spirodibenzopyranamines (eg according to WO 2013/083216) and dihydroacridine derivatives (eg according to WO 2012 /150001). The compounds of the present invention can also be used as hole transport materials.

The cathode of the organic electroluminescent device preferably contains a metal with a low work function, various metals (such as alkaline earth metals, alkali metals, main group metals or lanthanides (such as Ca, Ba, Mg, Al, In, Mg, Yb , Sm, etc.)) metal alloy or multilayer structure. Alloys containing alkali metals or alkaline earth metals and silver, for example, alloys containing magnesium and silver are also suitable. In the case of a multilayer structure, in addition to these metals, other metals with relatively high work functions (such as Ag or Al) can also be used. In this case, a combination of metals, such as Ca/Ag, Mg/Ag, is generally used Or Ag/Ag. It is also preferable to introduce a thin interlayer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal fluorides or alkaline earth metal fluorides, and corresponding oxides or carbonates (such as LiF, Li ₂ O, BaF ₂ , MgO, NaF, CsF, Cs ₂ CO _3, etc.) . In addition, lithium 8-hydroxyquinoline (LiQ) can be used for this purpose. The layer thickness of this layer is preferably between 0.5 nm and 5 nm.

The anode preferably contains a material having a high work function. The anode preferably has a work function greater than 4.5 eV for vacuum. On the one hand, metals with high redox potentials (such as Ag, Pt or Au) are suitable for this purpose. On the other hand, metal/metal oxide electrodes (eg, Al/Ni/NiO _x , Al/PtO _x ) may also be preferred. For some applications, at least one electrode must be transparent or partially transparent to facilitate irradiation of organic materials (organic solar cells) or coupling out light (OLED, O-laser). The preferred anode material herein is a conductive mixed metal oxide. Particularly preferred is indium tin oxide (ITO) or indium zinc oxide (IZO). In addition, it is preferably a conductively doped organic material, specifically a conductively doped polymer.

The device is appropriately (according to the application) structured to provide contacts and ultimately seal, as the life of the device of the present invention is reduced in the presence of water and/or air.

In a preferred embodiment, the organic electroluminescent device of the present invention is characterized by coating one or more layers by sublimation method, wherein at an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar The material is applied by vapor deposition in a vacuum sublimation unit. However, the initial pressure here can also be even lower, for example less than 10 ^-7 mbar.

Also preferred are organic electroluminescent devices characterized by: coating one or more layers by means of OVPD (Organic Vapor Deposition) method or by means of carrier gas sublimation, wherein between 10 ^-5 mbar and 1 bar Apply the material under pressure. A special case of this method is the OVJP (Organic Vapor Jet Printing) method, where materials are directly applied via nozzles and the materials are thus structured (eg MS Arnold et al., Appl. Phys. Lett. 2008 , 92 , 053301).

Also preferred are organic electroluminescent devices characterized by, for example, by spin coating, or by any desired printing method (such as screen printing, flexographic printing, nozzle printing, or lithographic printing, but LITI (light-induced Thermal imaging, thermal transfer printing) or inkjet printing) produces one or more layers from solution. Soluble compounds of formula (I) are necessary for this purpose. High solubility can be achieved through suitable substitution of compounds.

Hybrid processes in which, for example, one or more layers are applied from solution and one or more other layers are applied by vapor deposition are also possible. Thus, for example, the emission layer can be applied from solution and the electron transport layer can be applied by vapor deposition.

Such methods are generally known to those skilled in the art and can be applied to organic electroluminescent devices containing the compounds of the present invention from there without the steps of the present invention.

According to the invention, electronic devices comprising one or more compounds of the invention can be used in displays, as light sources in lighting applications, and as light sources in medical and/or cosmetic applications, such as phototherapy.

The invention will now be explained in more detail by the following examples, without wishing to limit the invention to this.

A) Synthesis example A-1) Part 1 synthesis building component BB-I :

Mix 117.9 g (401 mmol) of starting material a , 100 g (401 mmol) of starting material b, and 203.1 g (882 mmol) of potassium phosphate monohydrate in 1.6 L of toluene/water/dioxane (2:1: 1) Medium and degassing. Palladium acetate (0.9 g, 4 mmol) and tri-o-tolylphosphine (2.44 g, 8 mmol) were added to the mixture and the mixture was stirred under reflux for 16 h. After cooling the mixture to room temperature, the phases were separated. The aqueous phase was further extracted with ethyl acetate (2×300 mL). The combined organic phase was washed several times with water, dried over sodium sulfate and finally removed in vacuo. The crude material was filtered through a plug of SiO ₂ /Al ₂ O ₃ using ethyl acetate as a solvent. After removing the solvent in vacuum, oil was obtained in quantitative yield.

The following compounds can be synthesized in a similar manner:

Synthesis of BB-II :

To a pre-cooled THF suspension (0°C, 1.5 L) of compound BB-I (135 g, 0.4 mol) and CeCl ₃ (199 g, 0.8 mol) was added MeMgCl (461 mL, 3 M in THF) dropwise , 1.38 mol). After the reaction was completed, saturated aqueous NH ₄ Cl solution was added to quench excess MeMgCl, and the organic phase was extracted three times with ethyl acetate. The organic portions were combined and washed successively with water and brine. The volatiles are removed in vacuum, thereby producing the desired product. 129 g (96 %).

The following compounds can be synthesized in a similar manner:

Synthesis of BB-III :

To a solution of compound BB-II (129 g, 383 mmol) in toluene (1 L) was added 50 g Amberlyst-15. The mixture was stirred at reflux overnight. The mixture was cooled to room temperature and Amberlyst-15 was filtered out. The solvent was removed in vacuo and the crude product was purified by column chromatography (SiO ₂ , heptane). Yield: 106.2 g (87%).

The following compounds can be synthesized in a similar manner:

Synthesis of BB-IV :

To a solution of compound BB-III (100 g, 314 mmol) in CH ₂ Cl ₂ (1.2 L) was added N-bromosuccinimide (55.83 g, 314 mmol) and HBr (32% solution in acetic acid , 0.5 mL). The reaction was heated at 30°C for 4 days. After the reaction was completed, Na ₂ S ₂ O ₃ (300 mL, saturated aqueous solution) was added and the mixture was vigorously stirred for 30 minutes. The phases are separated and the organic phase is washed several times with water. The solvent was removed in vacuo and the crude product was vigorously stirred with ethanol to produce a white solid. Yield: 119.8 g (96%).

The following compounds can be synthesized in a similar manner:

Synthetic intermediate BB-V :

酸及16.0 g (151 mmol)碳酸鈉混合於600 mL甲苯/二噁烷/水(2:1:2)中且脫氣。向混合物中添加四(三苯基膦)鈀(2.2 g, 1.9 mmol)且將混合物於回流下攪拌4 h。在將混合物冷卻至室溫後，添加400 mL乙酸乙酯且分離各相。將有機相用水洗滌多次且在真空中去除溶劑。其後，使用乙酸乙酯作為溶劑經二氧化矽塞過濾有機相。在真空中去除溶劑且將粗產物與乙醇一起劇烈攪拌以產生白色固體。產量：28.3 g (95%)。30.0 g (75.4 mmol) BB-IV, 9.2 g (75.4 mmol) phenyl

The acid and 16.0 g (151 mmol) sodium carbonate were mixed in 600 mL toluene/dioxane/water (2:1:2) and degassed. To the mixture was added tetrakis(triphenylphosphine)palladium (2.2 g, 1.9 mmol) and the mixture was stirred under reflux for 4 h. After cooling the mixture to room temperature, 400 mL of ethyl acetate was added and the phases were separated. The organic phase was washed several times with water and the solvent was removed in vacuo. Thereafter, the organic phase was filtered through a silica plug using ethyl acetate as a solvent. The solvent was removed in vacuo and the crude product was vigorously stirred with ethanol to produce a white solid. Yield: 28.3 g (95%).

The following compounds can be synthesized in a similar manner:

A-2) Part 2 : Schematic synthesis example of compound 1.1

Synthesize BB-VI:

Combine 10-chloro-8,8-dimethyl-8H-5-oxa-indeno[2,1-c] stilbene (30.00 g; 94.1 mmol), bis-(pinacol)-diboron (28.68 g; 112.9 mmol) and potassium acetate (18.47 g; 188.2 mmol) were dissolved in 800 mL 1,4-dioxane.

The 3rd generation XPhos Palladacycle (CAS: 1445085-55-1; 1.59 g; 1.882 mmol) and bis-(pinacol)-diboron (28.68 g; 112.9 mmol) were added and the reaction mixture was stirred at 100° C. overnight. After complete conversion, the reaction mixture was cooled to room temperature and water and toluene were added. The phases are separated and the organic phase is washed several times with water. The organic phase was filtered and combined with silica using toluene as the eluent. The solvent was removed in vacuo and the crude product was vigorously stirred with ethanol to produce a white solid.

Yield: 34.2 g (83.4 mmol; 88%)

The following compounds can be synthesized in a similar manner:

BB-VII synthesis: BB-VII synthesis is similar to BB-I:

The following compounds can be synthesized in a similar manner:

BB-VIII synthesis: BB-VIII synthesis is similar to BB-II:

The following compounds can be synthesized in a similar manner:

BB-IX synthesis: BB-IX synthesis is similar to BB-III:

The following compounds can be synthesized in a similar manner:

Synthesis of intermediates BB-Xa and BB-Xb

The intermediates BB-X.a and BB-X.b can be synthesized in a similar manner to BB-IV.

Synthesis of intermediates BB-XI.a and BB-XI.b

酸酯起始材料來合成。BB-XI.a and BB-XI.b can be used in a similar way to BB-V by using CAS 1010100-76-1 as

It is synthesized from ester starting materials.

Synthesis of compound Int1.1 :

4.41 g (26.0 mmol) of biphenyl-2-ylamine, 11.31 g (26.0 mmol) of BB-IX and 6.82 g (70.9 mmol) of sodium tributoxide were mixed in 300 mL of toluene and degassed. Thereafter, 563 mg (1.4 mmol) S-Phos and 151 mg (0.7 mmol) palladium acetate were added and the mixture was stirred under reflux for 16 h. After cooling the mixture at room temperature, 200 mL of water was added and the phases were separated. The crude product was filtered through an alumina plug using toluene as a solvent. The product was further purified by recrystallization from toluene/heptane. Yield: 13.1 g (89%).

The following compounds can be synthesized in a similar manner:

A-3) Part 3

20.5 g (36.1 mmol) Int1.1, 14.3 g (36.1 mmol) BB-V and 20.9 g (217 mmol) sodium tributoxide were mixed in 700 mL toluene and degassed. Thereafter, 1.7 g (4.1 mmol) S-Phos and 455 mg (2.0 mmol) palladium acetate were added and the mixture was stirred under reflux for 16 h. After cooling the mixture at room temperature, 200 mL of water was added and the phases were separated. The crude product was filtered through an alumina plug using toluene as a solvent. The product was further purified by recrystallization from toluene/heptane to a purity of >99.9% by HPLC. Yield: 12.4 g (37%).

The following compounds can be synthesized in a similar manner:

B) Production of OLED The production of solution-based OLED has been described many times in the literature, for example in WO 2004/037887 and WO 2010/097155. This process is suitable for the following situations (layer thickness change, material).

The material combinations of the present invention are used in the following order: -Substrate, -ITO (50 nm), -Buffer (40 nm), -Emission layer (EML) (40 nm), -Hole Blocking Layer (HBL) (10 nm) -Electron Transport Layer (ETL) (30 nm), -Cathode (Al) (100 nm).

A glass plate coated with structured ITO (indium tin oxide) with a thickness of 50 nm is used as the substrate. The substrates were coated with buffer (PEDOT) Clevios P VP AI 4083 (Heraeus Clevios GmbH, Leverkusen). From the water in the air, the buffer solution is spin-coated. The layer was then dried by heating at 180°C for 10 minutes. The emissive layer is applied to the glass plate coated in this way.

The emission layer (EML) is composed of a host material (host material) H and an emission dopant (emitter) D. Both materials are stored in the emitting layer at a ratio of 97% by weight H and 3% by weight D. The mixture of emission layers was dissolved in toluene. If, as shown in this article, a layer thickness of 40 nm is to be achieved by spin coating (this is typical for devices), the solid content of these solutions is about 9 mg/ml. The layers were applied by spin coating in an inert gas atmosphere and dried by heating at 120°C for 10 minutes. The materials used in this case are shown in Table A. Table A: Structural formula of materials treated by solution in EML

The materials of the hole blocking layer and the electron transport layer were also applied by vapor deposition in a vacuum chamber and are shown in Table B. The hole blocking layer (HBL) consists of ETM. The electron transport layer (ETL) is composed of two materials, ETM and LiQ, which are mixed with each other by co-evaporation at a volume ratio of 50% each. The cathode is formed by thermal evaporation of an aluminum layer with a thickness of 100 nm. Table B: Structural formula of gas-treated OLED materials

Characterize OLED by standard methods. For this purpose, the electroluminescence spectrum was recorded, and the current efficiency (measured in cd/A) as a function of the luminous density of the assumed Lambert emission characteristic was calculated from the current/voltage/luminous density characteristic line (IUL characteristic line) and External quantum efficiency (EQE, measured in percentage). The electroluminescence spectrum was recorded at a luminous density of 1000 cd/m² and the CIE 1931 x and y color coordinates were calculated from this data. The term EQE1000 denotes the external quantum efficiency at an operating luminous density of 1000 cd/m².

表C顯示使用本發明之材料(D1、D2及D3)當用作螢光藍色發射體時，具體而言關於效率相對於先前技術(SdT1及SdT2)產生改良。The properties of various OLEDs are summarized in Table C. Examples V1 and V2 are comparative examples, while E3, E4 and E5 show the properties of OLEDs containing the material of the invention. Table C: Device data of solution-treated OLED

Table C shows that using the materials of the present invention (D1, D2, and D3) when used as fluorescent blue emitters, specifically with regard to efficiency, yields improvements over the prior art (SdT1 and SdT2).

Claims (17)

A compound of formula (1),

The following applies to the symbols and subscripts used: Ar ¹ and Ar ^N are the same or different at each occurrence and are selected from aromatic or heteroaromatic ring systems with 5 to 60 aromatic ring atoms, which in each case The following may be substituted by one or more groups R; E ¹ is selected from -BR ⁰ -, -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -O-, -C(R ⁰ ) ₂ -S-, -R ⁰ C=CR ⁰ -, -R ⁰ C=N-, Si(R ⁰ ) ₂ , -Si(R ⁰ ) ₂ -Si(R ⁰ ) ₂ -, -C(=O)-, -C(=NR ⁰ )-, -C(=C(R ⁰ ) ₂ )-, -O-, -S-, -S(=O)-, -SO ₂ -, -N(R ⁰ )-, -P(R ⁰ )- and -P((=O)R ⁰ )-; or E ¹ system The group of (E-1),

Where the symbol * in formula (E-1) indicates the corresponding group E ¹ in formula (1); and E ⁰ is selected from the group consisting of: single bond, -BR ^0- , -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -O-, -C(R ⁰ ) ₂ -S-, -R ⁰ C=CR ⁰ -, -R ⁰ C=N-, Si(R ⁰ ) ₂ , -Si(R ⁰ ) ₂ -Si(R ⁰ ) ₂ -, -C(=O)-, -C(= NR ⁰ )-, -C(=C(R ⁰ ) ₂ )-, -O-, -S-, -S(=O)-, -SO ₂ -, -N(R ⁰ )-, -P( R ⁰ )- and -P((=O)R ⁰ )-; E ² is selected from the group consisting of: -O-, -S-, -S(=O)- And -SO ₂ -; R ⁰ to R ⁵ represent H, D, F, Cl, Br, I, CHO, CN, N(Ar) ₂ , C(=O)Ar, P(=O)(Ar) ₂ , S(=O)Ar, S(=O) ₂ Ar, NO ₂ , Si(R) ₃ , B(OR) ₂ , OSO ₂ R; with 1 to 40 C Atom straight-chain alkyl, alkoxy or thioalkyl or branched or cyclic alkyl, alkoxy or thioalkyl having 3 to 40 C atoms, each of which may be composed of one or more groups Group R, where in each case one or more non-adjacent CH ₂ groups can be replaced by RC=CR, C≡C, Si(R) ₂ , Ge(R) ₂ , Sn(R) ₂ , C=O , C=S, C=Se, P(=O)(R), SO, SO ₂ , O, S or CONR, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN Or NO ₂ substitution; an aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R in each case; or having 5 to 60 aromatic ring atoms Aryloxy group, which may be substituted by one or more groups R, wherein two adjacent substituents R ⁰ , and/or two adjacent substituents R ¹ , and/or two adjacent substituents R ² , and/ Or two adjacent substituents R ³ , and/or two adjacent substituents R ⁴ , and/or two adjacent substituents R ⁵ may form a monocyclic or polycyclic, aliphatic ring system, or aromatic ring system, which may be One or more groups R are substituted; m at each occurrence is the same or different represents an integer selected from 0, 1 or 2; n, q at each occurrence is the same or different represents selected from 0, 1, 2 , 3 or 4 integer; p in each occurrence is the same or different represents an integer selected from 0, 1, 2 or 3; R in each occurrence is the same or different represents H, D, F , Cl, Br, I, CHO, CN, N(Ar) ₂ , C(=O)Ar, P(=O)(Ar) ₂ , S(=O)Ar, S(=O) ₂ Ar, NO ₂ , Si(R') ₃ , B(OR') ₂ , OSO ₂ R ^' ; linear alkyl, alkoxy or thioalkyl having 1 to 40 C atoms or having 3 to 40 C atoms The branched or cyclic alkyl, alkoxy or thioalkyl groups, each of which may be substituted by one or more groups R′, wherein in each case one or more non-adjacent CH ₂ groups may be substituted by R 'C=CR', C≡C, Si(R') ₂ , Ge(R') ₂ , Sn(R') ₂ , C=O, C=S, C=Se, P(=O)(R '), SO, SO ₂ , O, S or CONR' and one or more of the H atoms can be replaced by D, F, Cl, Br, I, CN or NO ₂ ; with 5 to 60 aromatic ring atoms Aromatic or heteroaromatic ring systems, which in each case may be substituted by one or more groups R'; or aryloxy groups having 5 to 60 aromatic ring atoms, which may be substituted by one or more groups R'substitution, where two adjacent substituents R can form a monocyclic or polycyclic, aliphatic ring system or aromatic ring system, which can be substituted by one or more groups R'; Ar system has 5 to 24 aromatic Aromatic or heteroaromatic ring systems of ring atoms, which in each case can also be substituted by one or more groups R′; R ^′ represents H, D, F, Cl, Br, I, CN; linear alkyl, alkoxy or thioalkyl having 1 to 20 C atoms or branched or cyclic alkyl, alkoxy or sulfur having 3 to 20 C atoms Substituted alkyl, wherein in each case one or more non-adjacent CH ₂ groups can be replaced by SO, SO ₂ , O, S and one or more H atoms can be replaced by D, F, Cl, Br or I; Or an aromatic or heteroaromatic ring system with 5 to 24 C atoms. The compound as claimed in claim 1, wherein Ar ^N represents phenyl, biphenyl, stilbene, spiro difutilene, naphthalene, phenanthrene, dibenzofuran, dibenzothiophene, carbazole, pyridine, pyrimidine, pyrazine, pyrazine, Triazine, benzopyridine, benzoxazine, benzopyrimidine, or quinazoline, or a combination of two to six of these groups, each of which may be substituted with one or more groups R. A compound as claimed in claim 1 or 2, wherein Ar ^N represents phenyl, biphenyl, stilbene, naphthalene, phenanthrene, dibenzofuran, dibenzothiophene, carbazole or two to six of these groups In combination, each of them may be substituted with one or more groups R. The compound according to claim 1, wherein it is selected from compounds of formula (2),

The symbols Ar ^N , E ¹ , E ² , Ar ¹ , R ¹ to R ⁵ and the subscripts m, n, p, and q have the same meanings as in claim 1. If the compound of claim 1, it is selected from compounds of formula (3),

The symbols Ar ^N , E ² , Ar ¹ , R ⁰ , R ¹ to R ⁵ and the subscripts m, n, p, and q have the same meanings as in claim 1. The compound of claim 1, which is selected from compounds of formula (4),

The symbols Ar ^N , E ² , Ar ¹ , R ⁰ , R ¹ to R ⁵ and the subscripts m, n, p, and q have the same meanings as in claim 1. The compound according to claim 1, wherein it is selected from compounds of formulae (4-1) to (4-4),

The symbols Ar ^N , E ² , Ar ¹ , R ⁰ , R ¹ to R ⁵ have the same meanings as in claim 1. The compound according to claim 1, wherein it is selected from formulas (4-1a) to (4-4a),

The symbols Ar ^N , E ² , Ar ¹ , R ⁰ and R ¹ have the same meanings as in claim 1. The compound according to claim 1, wherein it is selected from formulas (4-1b) to (4-4b),

The symbols Ar ^N , E ² , Ar ¹ and R ⁰ have the same meanings as in claim 1. The compound according to any one of claims 1 to 9, wherein E ² represents O. A compound as claimed in any one of claims 1 to 9, wherein Ar ¹ represents phenyl, biphenyl, stilbene, spirobifutene, naphthalene, phenanthrene, dibenzofuran, dibenzofuran at each occurrence Thiophene, carbazole, pyridine, pyrimidine, pyrazine, triazine, triazine, benzopyridine, benzopyrazine, benzopyrimidine, quinazoline, or a combination of two to six of these groups, which Each may be substituted by one or more groups R. The compound according to any one of claims 1 to 9, wherein Ar ¹ represents the aromatic or heteroaromatic ring system selected from the group consisting of phenyl, biphenyl, stilbene or naphthalene or A combination of two to six of these groups may be substituted by one or more groups R. The compound according to any one of claims 1 to 9, wherein Ar ¹ is a group selected from the group consisting of formulas (Ar1-1) to (Ar1-22),

Among them in formulas (Ar1-1) to (Ar1-22): the dotted bond indicates the bonding with the structure of formula (1); the group R ^N in formula (Ar1-14) is the same or different each time it appears Denotes H and D; linear alkyl having 1 to 40, preferably 1 to 20, more preferably 1 to 10 C atoms or 3 to 40, preferably 3 to 20, more preferably 3 to 10 C atoms Each of the branched or cyclic alkyl groups may be substituted by one or more groups R, wherein in each case one or more non-adjacent CH ₂ groups may be replaced by RC=CR, C≡C, C=O , C=S, SO, SO ₂ , O or S, and one or more H atoms can be replaced by D, F or CN; having 5 to 60, preferably 5 to 40, more preferably 5 to 30, particularly preferably An aromatic or heteroaromatic ring system of 5 to 18 aromatic ring atoms, which in each case may be substituted by one or more groups R, where two adjacent substituents R ^N may form a monocyclic or polycyclic, An aliphatic ring system or an aromatic ring system, which may be substituted by one or more groups R, where R has the same meaning as in claim 1; formulas (Ar1-12) and (Ar1-19) to (Ar1-22 ) In the group R ^0a has the same definition as the group R ⁰ as defined in claim 1; and groups of formula (Ar1-1) to (Ar1-22) can be defined by the group at each free position R is substituted and the group R has the same meaning as in claim 1. A polymer, oligomer or dendrimer containing one or more compounds as claimed in claim 1, wherein the bond to the polymer, oligomer or dendrimer can be located in formula (1) by R ⁰ , R ¹ , R ² , R ³ , R ⁴ or R ⁵ any position substituted. A formulation comprising at least one compound as claimed in any one of claims 1 to 13 or at least one polymer, oligomer or dendrimer as claimed in claim 14 and at least one solvent. An electronic device comprising at least one compound as claimed in any one of claims 1 to 13 or at least one polymer, oligomer or dendrimer as claimed in claim 14, the electronic device is selected from the group consisting of : Organic electroluminescence devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light-emitting transistors, organic solar cells, dye-sensitized organic solar cells, organic optical detectors, organic photoreceptors, Airport quenching devices, light-emitting electrochemical cells, organic laser diodes, and organic plasma emission devices. The electronic device according to claim 16, which is an organic electroluminescence device, wherein the compound according to any one of claims 1 to 13 or the polymer, oligomer, or dendrimer according to claim 14 is used as fluorescent light Emitters or matrix materials used as fluorescent emitters.